U.S. patent application number 16/982952 was filed with the patent office on 2021-03-11 for luminescent compounds.
The applicant listed for this patent is THE UNIVERSITY OF BIRMINGHAM. Invention is credited to Michael BUTLIN, Owen JONES, Gregory O'CALLAGHAN, Jon PREECE, Alex ROBINSON, Sareena SUND, Karolis VIRZBICKAS, Dennis ZHAO.
Application Number | 20210070720 16/982952 |
Document ID | / |
Family ID | 1000005288034 |
Filed Date | 2021-03-11 |
![](/patent/app/20210070720/US20210070720A1-20210311-C00001.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00002.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00003.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00004.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00005.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00006.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00007.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00008.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00009.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00010.png)
![](/patent/app/20210070720/US20210070720A1-20210311-C00011.png)
View All Diagrams
United States Patent
Application |
20210070720 |
Kind Code |
A1 |
ROBINSON; Alex ; et
al. |
March 11, 2021 |
LUMINESCENT COMPOUNDS
Abstract
Polycyclic aromatic hydrocarbons represented by the following
general formula (I) wherein X is one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium, tellurium; R
independently represents an aromatic group and/or an aliphatic
group; Q is one of a cyclic aliphatic hydrocarbon, a cyclic
aromatic hydrocarbon, a polycyclic hydrocarbon, a polycyclic
aromatic hydrocarbon, and/or a fused polycyclic aromatic
hydrocarbon; wherein the substituents independently comprise one or
more of a hydrogen atom, a deuterium atom, a fluorine atom, a
chlorine atom, a bromine atom, a carbon atom, an oxygen atom (e.g.
an alkylated oxygen atom), a nitrogen atom (e.g. an alkylated
nitrogen atom), a cyano group, a nitro group, an alkyl group and/or
anaryl group; p is an integer of 1 to 2; q is an integer of 1 to 4;
Y.sup.1 and Y.sup.2 independently represent one or more of a
hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom,
a bromine atom, a carbon atom, an oxygen atom (e.g. an alkylated
oxygen atom), a nitrogen atom (e.g. an alkylated nitrogen 20 atom),
a cyano group, a nitro group, an alkyl group and/oranaryl group;
and x is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more.
##STR00001##
Inventors: |
ROBINSON; Alex; (Birmingham,
West Midlands, GB) ; PREECE; Jon; (Birmingham, West
Midlands, GB) ; O'CALLAGHAN; Gregory; (Birmingham,
West Midlands, GB) ; VIRZBICKAS; Karolis;
(Birmingham, West Midlands, GB) ; JONES; Owen;
(Birmingham, West Midlands, GB) ; ZHAO; Dennis;
(Birmingham, West Midlands, GB) ; BUTLIN; Michael;
(Birmingham, West Midlands, GB) ; SUND; Sareena;
(Birmingham, West Midlands, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THE UNIVERSITY OF BIRMINGHAM |
Birmingham, West Midlands |
|
GB |
|
|
Family ID: |
1000005288034 |
Appl. No.: |
16/982952 |
Filed: |
March 21, 2019 |
PCT Filed: |
March 21, 2019 |
PCT NO: |
PCT/GB2019/050806 |
371 Date: |
September 21, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 51/0071 20130101;
H01L 51/5012 20130101; C07D 277/60 20130101 |
International
Class: |
C07D 277/60 20060101
C07D277/60; H01L 51/00 20060101 H01L051/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 21, 2018 |
GB |
1804512.0 |
Claims
1-34. (canceled)
35. Polycyclic aromatic hydrocarbons represented by the following
general formula: ##STR00022## wherein X is one of nitrogen,
phosphorus, arsenic, antimony, bismuth, sulphur, selenium,
tellurium; R independently represents an aromatic group and/or an
aliphatic group; Q is one of a cyclic aliphatic hydrocarbon, a
cyclic aromatic hydrocarbon, a polycyclic hydrocarbon, a polycyclic
aromatic hydrocarbon, and/or a fused polycyclic aromatic
hydrocarbon; wherein the substituents independently comprise one or
more of a hydrogen atom, a deuterium atom, a fluorine atom, a
chlorine atom, a bromine atom, a carbon atom, an oxygen atom, a
nitrogen atom, a cyano group, a nitro group, an alkyl group and/or
an aryl group; p is an integer of 1 to 2; q is an integer of 1 to
4; Y.sup.1 and Y.sup.2 independently represent one or more of a
hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom,
a bromine atom, a carbon atom, an oxygen atom, a nitrogen atom, a
cyano group, a nitro group, an alkyl group and/or an aryl group;
and x is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or
more.
36. The polycyclic aromatic hydrocarbon derivatives according to
claim 35, represented by the following general formula (B):
##STR00023## wherein X is one of nitrogen, phosphorus, arsenic,
antimony, bismuth, sulphur, selenium or tellurium; R independently
represents an aromatic group and/or an aliphatic group; p is an
integer of 1 to 2; q and s are independently integers of 1 to 4;
Y.sup.1, Y.sup.2, and Y.sup.3 independently represent a hydrogen
atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine
atom, a carbon atom, an oxygen atom, a nitrogen atom, a cyano
group, a nitro group, an alkyl group and/or an aryl group.
37. The polycyclic aromatic hydrocarbon derivatives according to
claim 36, wherein the polycyclic aromatic hydrocarbon derivatives
are triphenylene derivatives represented by the following general
formula: ##STR00024## wherein X is one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium or tellurium; R
independently represents an aromatic group and/or an aliphatic
group; A independently represents a hydrogen atom, an aryl group,
an alkyl group comprising 1 to 20 carbons or an alkyl ether; J
independently represent a hydrogen atom, a deuterium atom, a
fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom, a nitrogen atom, a cyano group, a nitro group, an
alkyl group and/or an aryl group.
38. The polycyclic aromatic hydrocarbons according to claim 36,
wherein the polycyclic aromatic hydrocarbon derivatives are
triphenylene derivatives represented by the following general
formula: ##STR00025## wherein X is independently one of nitrogen,
phosphorus, arsenic, antimony, bismuth, sulphur, selenium or
tellurium; R.sup.1 and R.sup.2 independently represents an aromatic
group and/or an aliphatic group; p and q are independently an
integer of 1 to 2; s is an integer of 1 to 4; Y.sup.1, Y.sup.2, and
Y.sup.3 independently represent a hydrogen atom, a deuterium atom,
a fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom, a nitrogen atom, a cyano group, a nitro group, an
alkyl group and/or an aryl group.
39. The polycyclic aromatic hydrocarbons according to claim 38,
wherein the polycyclic aromatic hydrocarbon derivatives are
triphenylene derivatives represented by the following general
formula: ##STR00026## wherein X is independently one of nitrogen,
phosphorus, arsenic, antimony, bismuth, sulphur, selenium or
tellurium; R.sup.1 and R.sup.2 independently represents an aromatic
group and/or an aliphatic group; A independently represents a
hydrogen atom, an aryl group, an alkyl group comprising 1 to 20
carbons or an alkyl ether; J independently represent a hydrogen
atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine
atom, a carbon atom, an oxygen atom, a nitrogen atom, a cyano
group, a nitro group, an alkyl group and/or an aryl group.
40. The polycyclic aromatic hydrocarbon derivatives according to
claim 36, represented by the following general formula:
##STR00027## wherein X is independently one of nitrogen,
phosphorus, arsenic, antimony, bismuth, sulphur, selenium or
tellurium; R.sup.1, R.sup.2, R.sup.3 independently represent an
aromatic group and/or an aliphatic group; p, q, and s are each
independently an integer of 1 to 2; Y.sup.1, Y.sup.2, and Y.sup.3
independently represent a hydrogen atom, a deuterium atom, a
fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom, a nitrogen atom, a cyano group, a nitro group, an
alkyl group and/or an aryl group.
41. The polycyclic aromatic hydrocarbons according to claim 40,
wherein the polycyclic aromatic hydrocarbon derivatives are
triphenylene derivatives represented by the following general
formula: ##STR00028## wherein X is independently one of nitrogen,
phosphorus, arsenic, antimony, bismuth, sulphur, selenium or
tellurium; R.sup.1, R.sup.2, R.sup.3 independently represent an
aromatic group and/or an aliphatic group; A independently
represents a hydrogen atom, an aryl group, an alkyl group
comprising 1 to 20 carbons or an alkyl ether; J independently
represent a hydrogen atom, a deuterium atom, a fluorine atom, a
chlorine atom, a bromine atom, a carbon atom, an oxygen atom, a
nitrogen atom, a cyano group, a nitro group, an alkyl group and/or
an aryl group.
42. The polycyclic aromatic hydrocarbons according to claim 36,
wherein X is a sulphur atom.
43. The polycyclic aromatic hydrocarbons according to claim 36,
wherein R comprises a phenyl group.
44. The polycyclic aromatic hydrocarbons according to claim 36,
wherein R comprises a heterocyclic group.
45. The polycyclic aromatic hydrocarbons according to claim 36,
wherein R comprise a polycyclic aromatic hydrocarbon.
46. The polycyclic aromatic hydrocarbons according to claim 45,
wherein R comprise one of naphthalene, anthracene, or pyrene.
47. The polycyclic aromatic hydrocarbons according to claim 36
selected from the structures Compound 1 and Compound 2.
##STR00029##
48. A device comprising the polycyclic aromatic hydrocarbons
according to claim 35.
49. A device according to claim 48, wherein the device is an
organic electroluminescent device, an OPV (organic photovoltaic)
device, a thin-film transistor, or a liquid crystal display.
50. A device of claim 49, wherein the organic electroluminescent
device comprises a pair of electrodes and one or more layers
interposed therebetween, wherein the one or more layers comprise
one or more of the polycyclic aromatic hydrocarbons.
51. A device of any of claim 48, wherein the polycyclic aromatic
hydrocarbon derivatives exhibit a Stokes shift of between 200
cm.sup.-1 to 36,000 cm.sup.-1.
52. A device of any of claim 48, wherein the polycyclic aromatic
hydrocarbon derivatives exhibit a conductivity value of
5.0.times.10.sup.-13 S cm.sup.-1 and 1.times.10.sup.2 S
cm.sup.-1.
53. A method of synthesising polycyclic aromatic hydrocarbon
derivatives (P2) according to the general formula: ##STR00030##
wherein (F2) represents the polycyclic aromatic hydrocarbon
starting material, (P2) represents the polycyclic aromatic
hydrocarbon derivative; G is a carbon atom; p is an integer of 1 to
2; q and s are integers of 1 to 4; Y.sup.1, Y.sup.2, and Y.sup.3
independently represent one or more of a hydrogen atom, a deuterium
atom, a fluorine atom, a chlorine atom, a bromine atom, a carbon
atom, an oxygen atom, a nitrogen atom, a cyano group, a nitro
group, an alkyl group and/or an aryl group; (E) represents the
reagent; R independently represents an aromatic group and/or an
aliphatic group; Z is one of an oxygen atom, a derivatised oxygen
atom, a chlorine atom, or a bromine atom, or any good leaving
group.
54. A method according to claim 53, wherein step (ii) further
comprises the use of a thiolating agent.
Description
[0001] This invention relates generally to organic luminescent
compounds. More specifically, although not exclusively, this
invention relates to novel luminescent polycyclic aromatic
hydrocarbon, e.g. triphenylene, derivatives, methods of
synthesising the same, uses of the same, and devices comprising the
same.
[0002] Luminescent compounds are widely used in industrial and
research applications as, for example, dyes, probes, sensors, and
in electronic devices. These molecules emit light under external
energy excitation from sources such as light and/or electrical
current.
[0003] In photoluminescence, under light irradiation a luminescent
compound will absorb light of a specific wavelength and re-emit
light of a different wavelength. The type of photoemission observed
depends on the molecular structure of the compound.
[0004] The difference between the maximum excitation wavelength and
the emission wavelength of a luminescent compound is known as the
Stokes shift. For use as dyes, probes and/or sensors in industrial
applications, it is advantageous for luminescent compounds to
possess a large Stokes shift, often defined as greater than 8000
cm.sup.-1 i.e. a comparatively large difference between the
excitation wavelength and emission wavelength. This is advantageous
because it minimises the reabsorption of light from the emission of
the molecule.
[0005] A drawback of many fluorescent dyes with large Stokes shifts
is their relatively low brightness, this being defined as the
product of the molar extinction coefficient and fluorescence
quantum yield. Additionally, dyes with large Stokes shifts often
suffer from poor photostability (Methods Appl. Fluoresc. 3 (2015)
042004).
[0006] Organometallic complexes that are luminescent often have a
large Stokes shift. However, these contain metal centres, e.g.
osmium, ruthenium, iridium, rhenium and so on, which are rare,
expensive, the complexes are often difficult to synthesise and
often toxic. Luminescent organic molecules are often easier to
synthesise, but usually exhibit a Stokes shift of relatively
smaller magnitude.
[0007] In contrast, in electroluminescence, a luminescent compound
will emit light in response to an electric current. One of the main
applications for this phenomenon is in electronic devices
containing OLEDs (Organic Light Emitting Diodes). The OLED material
is a layer of a luminescent organic compound, which is situated
between two electrodes, one of which is typically transparent. This
technology is used in digital displays in electronic devices such
as televisions screens, computer monitors, mobile phones,
electroluminescent lighting panels and so on.
[0008] It is advantageous for luminescent compounds for use in
electroluminescent applications to exhibit high brightness.
Brightness is defined as the product of the molar extinction
coefficient (E) and fluorescence quantum yield (.PHI.) divided by
1000. Consequently, it is advantageous for luminescent compounds to
exhibit a high molar extinction coefficient (E) (defined by the
Beer-Lambert law, in which A is absorbance, c is the molar
concentration of the luminescent compound, and l is the path
length), and also a high quantum yield (.PHI.) as a measure of
efficiency.
[0009] It is well known that polycyclic aromatic hydrocarbons
exhibit luminescent properties. One such class of compound is
triphenylene and its derivatives. For example, triphenylene may be
functionalised with alkoxy chains appended to the periphery of the
molecule. In addition, these derivatives exhibit discotic liquid
crystalline (DLC) behaviour (J. Nabar and A. Chodkowska, J.
Luminescence, 1975, 11, 215). Discotic liquid crystalline behaviour
is characterised in that disc-shaped molecules form stacks or
columns in a mesophase, which allows charge transfer through .pi.
stacking, enabling the material to be electrically semi-conductive
in the stacking direction. This DLC behaviour, combined with the
luminescent properties, is particularly useful for application in
technologies such as electronic devices using OLEDs (Organic Light
Emitting Diodes), LEDs (Light Emitting Diodes), and for use in
solar cells.
[0010] It is also known for luminescent compounds to exhibit
photoconductivity, in which compounds exhibit increased electrical
conductivity in the presence of light by converting the light
energy into current. It is known to utilise compounds with good
photoconductivity in devices such as solar cells.
[0011] Although many luminescent triphenylene derivatives have been
synthesised and characterised (Levell et. al. J. Phys. Chem. A.,
2010, 114, 13291, for example), it remains a challenge to provide
triphenylene derivatives with the advantageous properties described
above, i.e. large Stokes shift, high brightness, high molar
extinction coefficient, and high quantum yield. Furthermore, it
remains a challenge to provide a range of luminescent compounds
that emit wavelengths throughout the visible spectrum.
Specifically, blue emitters are a particular challenge to provide
(Chem Soc Rev. 2013 Jun. 21; 42(12):4963-76).
[0012] Furthermore, it remains a challenge to provide luminescent
triphenylene derivatives wherein the absorption and the emission
energies can be predicted and tuned by design and synthesis to
result in specific and desired visible colours (Methods Appl.
Fluoresc. 3 (2015) 042004).
[0013] Accordingly, a first aspect of the invention provides
polycyclic aromatic hydrocarbon derivatives represented by the
following general formula:
##STR00002## [0014] wherein X is one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium, tellurium; [0015] R
independently represents an aromatic group and/or an aliphatic
group; [0016] Q is one of a cyclic aliphatic hydrocarbon, a cyclic
aromatic hydrocarbon, a polycyclic hydrocarbon, a polycyclic
aromatic hydrocarbon, and/or a fused polycyclic aromatic
hydrocarbon; wherein the substituents independently comprise one or
more of a hydrogen atom, a deuterium atom, a fluorine atom, a
chlorine atom, a bromine atom, a carbon atom, an oxygen atom (e.g.
an alkylated oxygen atom), a nitrogen atom (e.g. an alkylated
nitrogen atom), a cyano group, a nitro group, an alkyl group and/or
[0017] an aryl group; [0018] p is an integer of 1 to 2; [0019] q is
an integer of 1 to 4; [0020] Y.sup.1 and Y.sup.2 independently
represent one or more of a hydrogen atom, a deuterium atom, a
fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom (e.g. an alkylated oxygen atom), a nitrogen atom (e.g.
an alkylated nitrogen atom), a cyano group, a nitro group, an alkyl
group and/or an aryl group; [0021] and x is an integer of 0, 1, 2,
3, 4, 5, 6, 7, 8, 9, 10 or more.
[0022] In embodiments, Q may represent C.sub.6H.sub.4. In
embodiments, Q is a polycyclic aromatic hydrocarbon, for example, Q
may be one of naphthalene, anthracene, phenanthrene, tetracene,
chrysene, triphenylene, pyrene, pentacene, benzo[a]pyrene,
corannulene, benzo[ghi]perylene, coronene, ovalene, fullerene,
and/or benzo[c]fluorene. Q may be any isomer of the polycyclic
aromatic hydrocarbons described, for example, 1-napthalene,
2-napthalene, 2-anthracene, 9-anthracene. The polycyclic aromatic
hydrocarbon group may be substituted with other moieties such as
aryl groups, alkyl groups, heteroatoms, and/or other electron
withdrawing or electron donating groups.
[0023] Q is bonded to other six membered rings, e.g. aromatic six
membered rings, and/or substituted aromatic six membered rings. The
number of six membered rings bonded to Q is represented by the
integer x wherein x is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or
more.
[0024] In an embodiment, Q is an aromatic six-membered ring, and x
is 2.
[0025] In embodiments, the polycyclic aromatic hydrocarbon
derivatives may be represented by the following general
formula:
##STR00003## [0026] wherein X is one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium, tellurium; [0027] D
is a hydrogen atom, a deuterium atom, a silicon atom, or a carbon
atom; [0028] p is an integer of 1 to 2; [0029] q is an integer of 1
to 2; [0030] Y.sup.1 and Y.sup.2 independently represent one or
more of a hydrogen atom, a deuterium atom, a fluorine atom, a
chlorine atom, a bromine atom, a carbon atom, an oxygen atom (e.g.
an alkylated oxygen atom), a nitrogen atom (e.g. an alkylated
nitrogen atom), a cyano group, a nitro group, an alkyl group and/or
an aryl group; [0031] and x is an integer of 0, 1, 2, 3, 4, 5, 6,
7, 8, 9, 10 or more.
[0032] For example, D may be a linear or branched alkyl chain, an
aryl group, or a combination thereof.
[0033] The polycyclic aromatic hydrocarbon derivatives may be
represented by the following general formula:
##STR00004## [0034] wherein X is one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium, tellurium; [0035] D
is a hydrogen atom, a deuterium atom, a silicon atom, or a carbon
atom; [0036] p is an integer of 1 to 2; [0037] q is an integer of
1; [0038] Y.sup.1 and Y.sup.2 independently represent one or more
of a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine
atom, a bromine atom, a carbon atom, an oxygen atom (e.g. an
alkylated oxygen atom), a nitrogen atom (e.g. an alkylated nitrogen
atom), a cyano group, a nitro group, an alkyl group and/or an aryl
group; [0039] and x is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9,
10 or more.
[0040] For example, D may be a linear or branched alkyl chain, an
aryl group, or a combination thereof.
[0041] A further aspect of the invention provides polycyclic
aromatic hydrocarbon derivatives, represented by the following
general formula:
##STR00005## [0042] wherein X is one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium or tellurium; [0043]
R independently represents an aromatic group and/or an aliphatic
group; [0044] p is an integer of 1 to 2; [0045] q and s are
independently integers of 1 to 4; [0046] Y.sup.1, Y.sup.2, and
Y.sup.3 independently represent a hydrogen atom, a deuterium atom,
a fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom (e.g. an alkylated oxygen atom), a nitrogen atom (e.g.
an alkylated nitrogen atom), a cyano group, a nitro group, an alkyl
group and/or an aryl group (e.g. a phenol group).
[0047] In embodiments, the polycyclic aromatic hydrocarbon
derivative may be a triphenylene derivative. In alternative
embodiments, the polycyclic aromatic hydrocarbon derivative may
comprise a fused polycyclic aromatic hydrocarbon comprising six
6-membered rings.
[0048] Y.sup.1, Y.sup.2, and Y.sup.3 may be one or more of hydrogen
atoms, deuterium atoms, oxygen atoms, fluorine atoms, chlorine
atoms, carbon atoms, cyano groups, nitro groups carboxylic acid
groups, glycol, alkoxy, thioalkoxy, amino, acetate, amide,
thioamide, thioester, azo, and/or silyl groups. Additionally or
alternatively, Y.sup.1, Y.sup.2, and Y.sup.3 may comprise an alkyl
group. The alkyl group(s) may be a straight chain, or may comprise
a branched chain, and/or may be further functionalised.
Additionally or alternatively, Y.sup.1, Y.sup.2, and Y.sup.3 may
comprise an aryl group, The aryl group(s) may be unsubstituted or
may be further functionalised. The integer p may be 1 to 2. The
integer q may be 1, 2, 3, or 4. The integer s may be 1, 2, 3, or
4.
[0049] A yet further aspect of the invention provides polycyclic
aromatic hydrocarbon derivatives, represented by the following
general formula:
##STR00006## [0050] wherein X is one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium or tellurium; [0051]
R independently represents an aromatic group and/or an aliphatic
group; [0052] q is independently an integer of 1 to 3; [0053] s is
independently an integer of 1 to 4; [0054] t is independently an
integer of 1 to 4; [0055] Y.sup.2, Y.sup.3, and Y.sup.4 and J
independently represent a hydrogen atom, a deuterium atom, a
fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom (e.g. an alkylated oxygen atom), a nitrogen atom (e.g.
an alkylated nitrogen atom), a cyano group, a nitro group, an alkyl
group and/or an aryl group (e.g. a phenol group).
[0056] In embodiments, the polycyclic aromatic hydrocarbon
derivatives are triphenylene derivatives, represented by the
following general formula:
##STR00007## [0057] wherein X is one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium or tellurium; [0058]
R independently represents an aromatic group and/or an aliphatic
group; [0059] A independently represents a hydrogen atom, an aryl
group, an alkyl group comprising 1 to 20 carbons (e.g. 1 to 15
carbons, or 1 to 10 carbons, or 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1
carbons) or an alkyl ether; [0060] J independently represent a
hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom,
a bromine atom, a carbon atom, an oxygen atom (e.g. an alkylated
oxygen atom), a nitrogen atom (e.g. an alkylated nitrogen atom), a
cyano group, a nitro group, an alkyl group and/or an aryl group
(e.g. a phenol group).
[0061] In embodiments, A may be C.sub.5H.sub.11 and/or
C.sub.4H.sub.9. In embodiments, A represents a polyethylene glycol
(PEG) group (e.g.
C.sub.2H.sub.4OC.sub.2H.sub.4OC.sub.2H.sub.4OCH.sub.3.
[0062] In embodiments, X is a sulphur atom.
[0063] In embodiments, the polycyclic aromatic hydrocarbons are
represented by the following general formula:
##STR00008## [0064] wherein X is independently one of nitrogen,
phosphorus, arsenic, antimony, bismuth, sulphur, selenium or
tellurium; [0065] R.sup.1 and R.sup.2 independently represents an
aromatic group and/or an aliphatic group; [0066] p and q are
independently an integer of 1 to 2; [0067] s is an integer of 1 to
4; [0068] Y.sup.1, Y.sup.2, and Y.sup.3 independently represent a
hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom,
a bromine atom, a carbon atom, an oxygen atom (e.g. an alkylated
oxygen atom), a nitrogen atom (e.g. an alkylated nitrogen atom), a
cyano group, a nitro group, an alkyl group and/or an aryl
group.
[0069] In embodiments, the polycyclic aromatic hydrocarbons are
triphenylene derivatives represented by the following general
formula:
##STR00009## [0070] wherein X is independently one of nitrogen,
phosphorus, arsenic, antimony, bismuth, sulphur, selenium or
tellurium; [0071] R.sup.1 and R.sup.2 independently represents an
aromatic group and/or an aliphatic group; [0072] A independently
represents a hydrogen atom, an aryl group, an alkyl group
comprising 1 to 20 carbons (e.g. 1 to 15 carbons, or 1 to 10
carbons, or 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 carbons) or an alkyl
ether; [0073] J independently represent a hydrogen atom, a
deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, a
carbon atom, an oxygen atom (e.g. an alkylated oxygen atom), a
nitrogen atom (e.g. an alkylated nitrogen atom), a cyano group, a
nitro group, an alkyl group and/or an aryl group.
[0074] In embodiments, A may be C.sub.5H.sub.11 and/or
C.sub.4H.sub.9. In embodiments, A represents a polyethylene glycol
(PEG) group (e.g.
C.sub.2H.sub.4OC.sub.2H.sub.4OC.sub.2H.sub.4OCH.sub.3.
[0075] In embodiments, the polycyclic aromatic hydrocarbons are
represented by the following general formula:
##STR00010## [0076] wherein X is independently one of nitrogen,
phosphorus, arsenic, antimony, bismuth, sulphur, selenium or
tellurium; [0077] R.sup.1, R.sup.2, R.sup.3 independently represent
an aromatic group and/or an aliphatic group; [0078] p, q, and s are
each independently an integer of 1 to 2; [0079] Y.sup.1, Y.sup.2,
and Y.sup.3 independently represent a hydrogen atom, a deuterium
atom, a fluorine atom, a chlorine atom, a bromine atom, a carbon
atom, an oxygen atom (e.g. an alkylated oxygen atom), a nitrogen
atom (e.g. an alkylated nitrogen atom), a cyano group, a nitro
group, an alkyl group and/or an aryl group.
[0080] In embodiments, the polycyclic aromatic hydrocarbons are
triphenylene derivatives represented by the following general
formula:
##STR00011##
[0081] wherein X is independently one of nitrogen, phosphorus,
arsenic, antimony, bismuth, sulphur, selenium or tellurium; [0082]
R.sup.1, R.sup.2, R.sup.3 independently represent an aromatic group
and/or an aliphatic group; A independently represents a hydrogen
atom, an aryl group, an alkyl group comprising 1 to 20 carbons
(e.g. 1 to 15 carbons, or 1 to 10 carbons, or 10, 9, 8, 7, 6, 5, 4,
3, 2 or 1 carbons) or an alkyl ether; [0083] J independently
represent a hydrogen atom, a deuterium atom, a fluorine atom, a
chlorine atom, a bromine atom, a carbon atom, an oxygen atom (e.g.
an alkylated oxygen atom), a nitrogen atom (e.g. an alkylated
nitrogen atom), a cyano group, a nitro group, an alkyl group and/or
an aryl group.
[0084] In embodiments, A comprises further functionality, for
example, A may further comprise fluorine atoms, chlorine atoms,
cyano groups, nitro groups, glycol, alkoxy, thioalkoxy,
polyethylene glycol, amino, acetate, carboxylic acid, amide,
thioamide, thioester, azo, and/or silyl groups.
[0085] In embodiments, X is a sulphur atom.
[0086] In embodiments, J comprises or represents an aryl group,
e.g. a phenol group. Additionally or alternatively, J comprises a
halogen atom, e.g. fluorine, chlorine, bromine, or iodine.
[0087] In embodiments, R, R.sup.1, R.sup.2, or R.sup.3 may be an
alkyl group, for example, a straight or branched alkyl chain. In
embodiments, at least one of R, R.sup.1, R.sup.2, R.sup.3 may be a
methyl, ethyl, propyl, butyl group.
[0088] The group R, R.sup.1, R.sup.2, or R.sup.3, may independently
be an aromatic group and/or an aliphatic group.
[0089] In embodiments wherein R, R.sup.1, R.sup.2, or R.sup.3 is an
aromatic group, the aromatic group may be one of, or a combination
of, an aromatic hydrocarbon group, and/or an aromatic heterocyclic
group.
[0090] In embodiments wherein R, R.sup.1, R.sup.2, or R.sup.3 is an
aromatic hydrocarbon group, the aromatic hydrocarbon group may
comprise one of, or a combination of, a phenyl ring and/or a
substituted phenyl ring. There may be one, two, three, four, or
five additional substituents on the phenyl ring. The substituents
are bonded directly to the phenyl ring, and may be one of, or a
combination of, fluorine, chlorine, bromine, iodine, a hydroxyl
group, an amine group, a nitro group, an alkoxy group, a carboxylic
acid, an amide, a cyano group, a trifluoromethyl, an ester, an
alkene an alkyne, an azide, an azo, an isocyanate, a ketone, an
aldehyde, an alkyl group consisting of a hydrocarbon chain, or a
hydrocarbon ring, an alkyl group consisting of other heteroatoms
such as fluorine, chlorine, bromine, iodine, oxygen, nitrogen,
and/or sulphur. The alkyl group may comprise a hydroxyl group, an
amine group, a nitro group, an ether group, a carboxylic acid, an
amide, a cyano group, trifluoromethyl, an ester, an alkene an
alkyne, an azide, an azo, an isocyanate, a ketone, an aldehyde, for
example. The substituents may be another aromatic group, for
example, R may comprise a phenyl substituted with a further phenyl
ring. In embodiments, the R group may be a phenyl ring, substituted
with a second phenyl ring, which in turn is substituted with a
third phenyl ring.
[0091] In embodiments wherein R, R.sup.1, R.sup.2, or R.sup.3 is an
aromatic group, the aromatic group may be a polycyclic aromatic
hydrocarbon, for example, naphthalene, anthracene, phenanthrene,
tetracene, chrysene, triphenylene, pyrene, pentacene,
benzo[a]pyrene, corannulene, benzo[ghi]perylene, coronene, ovalene,
fullerene, and/or benzo[c]fluorene. The R group may be bonded to
the polycyclic aromatic hydrocarbon derivative, e.g. the
triphenylene derivative, by any isomer of the polycyclic aromatic
hydrocarbons described, for example, 1-napthalene, 2-napthalene,
2-anthracene, 9-anthracene. The polycyclic aromatic hydrocarbon
group may be substituted with other moieties such as aryl groups,
alkyl groups, heteroatoms, and/or other electron withdrawing or
electron donating groups.
[0092] In embodiments, wherein R, R.sup.1, R.sup.2, or R.sup.3 is
an aromatic heterocyclic group, the heterocyclic group may be a
three membered ring, a four membered ring, a five membered ring, a
six membered ring, a seven membered ring, an eight membered ring, a
nine membered ring, a ten membered ring, or a fused ring. In
embodiments, the heterocyclic group may be furan, benzofuran,
isobenzofuran, pyrrole, indole, isoindole, thiophene,
benzothiophene, benzo[c]thiophene, imidazole, benzimidazole,
purine, pyrazole, indazole, oxazole, benzoxazole, isoxazole,
benzisoxazole, thiazole, benzothiazole, pyridine, quinoline,
isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine,
quinozoline, pyridazine, cinnoline, phthalazine, 1,2,3-triazine,
1,2,4-triazine, 1,3,5-triazine, pyridine or thiophene.
[0093] In embodiments wherein R, R.sup.1, R.sup.2, or R.sup.3 is an
aliphatic group, the aliphatic group may be one of, or a
combination of, an n-alkyl chain, a branched alkyl chain, an alkyl
chain comprising unsaturated moieties, an alkyl chain comprising
heteroatoms, for example, fluorine, chlorine, bromine, iodine,
oxygen, sulphur, nitrogen. The alkyl chain may comprise unsaturated
portions, comprising alkenes, or aromatic moieties. The alkyl chain
may comprise functional groups for further derivatisation of the
polycyclic aromatic hydrocarbon derivative, e.g. the triphenylene
derivative. For example, the functional groups may be one or more
of an azide, a carbonyl group, an alcohol, a halogen, or an
alkene.
[0094] The polycyclic aromatic hydrocarbon, e.g. triphenylene,
derivatives may be used, for example, as luminescent dyes for use
in devices.
[0095] A further aspect of the invention provides a device
comprising the polycyclic aromatic hydrocarbon, e.g. triphenylene,
derivatives. The device may be an electronic device, for example,
an organic electroluminescent device, a thin-film transistor and/or
an OPV (organic photovoltaic) device. The electronic device may
comprise a digital display, the digital display comprising
polycyclic aromatic hydrocarbon, e.g. triphenylene, derivatives of
the present invention, for example, a liquid crystal display. The
digital display may be in a television screen, a computer monitor,
a mobile phone screen, a games console, for example. The organic
electroluminescent device may comprise a pair of electrodes and one
or more layers interposed therebetween, wherein the one or more
layers comprise one or more of the polycyclic aromatic hydrocarbon,
e.g. triphenylene, derivatives.
[0096] The device may be for the use of detecting species, for
example, ions, e.g. metal ions. For example, the polycyclic
aromatic hydrocarbon derivative, e.g. the triphenylene derivative,
may comprise a moiety that is capable of binding to a species, e.g.
an ion. The moiety may be tagged to or integrated into, i.e.
covalently bonded to, the polycyclic aromatic hydrocarbon
derivative, e.g. the triphenylene derivative. Binding of a species
to a polycyclic aromatic hydrocarbon derivative, e.g. a
triphenylene derivative, may elicit a luminescent response. The
luminescent response may be recorded to quantitatively or
qualitatively measure the presence of the species, e.g. in
solution. The moiety may be a crown ether, a multidentate ligand, a
bidentate ligand or a monodentate ligand. The polycyclic aromatic
hydrocarbon, e.g. triphenylene, derivative, e.g. comprising a
moiety that is capable of binding to a species, may be spin coated
onto a dipstick. The dipstick may comprise a UV LED (light emitting
diode). The LED may be illuminated in the presence of specific
species upon binding to the polycyclic aromatic hydrocarbon, e.g.
triphenylene, derivative, e.g. ions, metal ions. The LED
illumination may be specific to a specific species that is bound to
the polycyclic aromatic hydrocarbon, e.g. triphenylene, derivative,
i.e. a specific wavelength of light, wavelength A, is emitted by
the LED upon binding to a specific species, species A, and a
different wavelength of light, wavelength B, is emitted by the LED
upon binding to a specific species, species B.
[0097] The device may be used in biofluorescent microscopy
techniques. The device may comprise the polycyclic aromatic
hydrocarbon, e.g. triphenylene, derivatives as a luminescent dye
that may be used to label biological, or non-biological samples,
which may include DNA or proteins or antigens or biomarkers.
[0098] The device may comprise a polymer, or a pre-polymer, and/or
a resin composition for use in printing, for example, for use in 3D
printing plastic products comprising the polycyclic aromatic
hydrocarbon, e.g. triphenylene, derivatives. The polycyclic
aromatic hydrocarbon, e.g. triphenylene, derivatives may be used as
a dopant in the device.
[0099] The polycyclic aromatic hydrocarbon, e.g. triphenylene,
derivative(s) of the device may emit light in the visible spectrum,
i.e. between 380 nm and 750 nm. The triphenylene derivative(s) of
the device may exhibit a Stokes shift of between 8000 cm.sup.-1 to
25,000 cm.sup.-1, for example, between 15,000 cm.sup.-1 to 25,000
cm.sup.-1. The polycyclic aromatic hydrocarbon derivatives, e.g.
triphenylene derivative(s), of the device may exhibit a
conductivity value of 5.0.times.10.sup.-13 S cm.sup.-1 and
1.5.times.10.sup.-11 S cm.sup.-1, for example, between
6.times.10.sup.-12 S cm.sup.-1 and 1.5.times.10.sup.-11 S
cm.sup.-1. The polycyclic aromatic hydrocarbon, e.g. triphenylene,
derivative(s) of the device may) exhibit a photoconductivity when
irradiated at 350 nm of between 1.5.times.10.sup.-10 S cm.sup.-1
and 1.times.10.sup.-3 5 cm.sup.-1, for example, between
1.times.10.sup.-8 S cm-1 and 1.times.10.sup.-3 cm.sup.-1.
[0100] A yet further aspect of the invention provides a method of
synthesising polycyclic aromatic hydrocarbons, e.g. triphenylene
derivatives, (P1) comprising the general formula:
##STR00012## [0101] wherein R independently represents an aromatic
group and/or an aliphatic group; [0102] p is an integer of 1 to 2;
[0103] q and s are independently integers of 1 to 4; [0104]
Y.sup.1, Y.sup.2, and Y.sup.3 independently represent a hydrogen
atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine
atom, a carbon atom, an oxygen atom (e.g. an alkylated oxygen
atom), a nitrogen atom (e.g. an alkylated nitrogen atom), a cyano
group, a nitro group, an alkyl group and/or an aryl group (e.g. a
phenol group).
[0105] In embodiments, the polycyclic aromatic hydrocarbon
derivative may be a triphenylene derivative.
[0106] In this embodiment, (SM1) represents a polycyclic aromatic
hydrocarbon core and (P1) represents a polycyclic aromatic
hydrocarbon derivative. A' may be an alkyl chain, for example, an
alkyl chain comprising three or more carbon atoms, e.g. four, five,
six, seven, or more carbon atoms. The method may involve the
polycyclic aromatic hydrocarbon core (SM1) undergoing an
intramolecular rearrangement to produce a polycyclic aromatic
hydrocarbon derivative (P1).
[0107] A yet further aspect of the invention provides a method of
synthesising polycyclic aromatic hydrocarbon derivatives, e.g.
triphenylene derivatives, (P2) comprising the general formula:
##STR00013##
wherein (F2) represents the polycyclic aromatic hydrocarbon
starting material, (P2) represents the polycyclic aromatic
hydrocarbon derivative; G is a carbon atom, e.g. an alkyl chain, or
an aryl group; p is an integer of 1 to 2; q and s are integers of 1
to 4; Y.sup.1, Y.sup.2, and Y.sup.3 independently represent one or
more of a hydrogen atom, a deuterium atom, a fluorine atom, a
chlorine atom, a bromine atom, a carbon atom, an oxygen atom (e.g.
an alkylated oxygen atom), a nitrogen atom (e.g. an alkylated
nitrogen atom), a cyano group, a nitro group, an alkyl group and/or
an aryl group; (E) represents the reagent; R independently
represents an aromatic group and/or an aliphatic group; Z is one of
an oxygen atom, a derivatised oxygen atom, a chlorine atom, or a
bromine atom, or any good leaving group.
[0108] Compound (F2) represents the polycyclic aromatic hydrocarbon
core, wherein group G may be a carbon atom, e.g. an alkyl chain, or
an aryl group. (E) represents the reagent, wherein R is an aromatic
group and/or an aliphatic group, and group Z may be one of an
oxygen atom, a derivatised oxygen atom, e.g. an OH group; a
chlorine atom, or a bromine atom, or any good leaving group.
Reagent (E) may be an acyl chloride or a carboxylic acid. The
method may involve Step (i) the polycyclic aromatic hydrocarbon
core (F2) and the reagent (E) undergoing an intermolecular coupling
reaction to produce the polycyclic aromatic hydrocarbon
intermediate (G2). The polycyclic aromatic hydrocarbon intermediate
(G2) may undergo Step (ii) a thionation reaction followed by an
intramolecular cyclisation reaction to afford the polycyclic
aromatic hydrocarbon derivatives (P2).
[0109] In embodiments, the polycyclic aromatic hydrocarbon
derivative (P2) may be a triphenylene derivative.
[0110] Step (ii) of the method may be performed using a thionating
agent, for example, Lawesson's reagent, ammonium phosphorodithioate
or thiophosphoryl chloride with triethylamine.
[0111] The method of synthesising triphenylene derivatives (P3) may
comprise the general formula:
##STR00014## [0112] wherein (F3) represents a triphenylene core,
(P3) represents a triphenylene derivative; [0113] A independently
represents a hydrogen atom, an aryl group, an alkyl group
comprising 1 to 20 carbons (e.g. 1 to 15 carbons, or 1 to 10
carbons, or 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 carbons); [0114] J
independently represent a hydrogen atom, a deuterium atom, a
fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom (e.g. an alkylated oxygen atom), a nitrogen atom (e.g.
an alkylated nitrogen atom), a cyano group, a nitro group, an alkyl
group and/or an aryl group. [0115] G is a carbon atom; [0116] (E)
represents the reagent; [0117] R independently represents an
aromatic group and/or an aliphatic group; [0118] Z is one of an
oxygen atom, a derivatised oxygen atom, a chlorine atom, or a
bromine atom, or any good leaving group.
[0119] (F3) represents the triphenylene core, G may be an alkyl or
aryl group, (E) represents the reagent, R is an aromatic group
and/or an aliphatic group, Z is one of an oxygen atom, e.g. an OH
group, a derivatised oxygen atom, a chlorine atom, or a bromine
atom, or any good leaving group, and wherein the triphenylene core
(F3) and the reagent (E) undergo Step (i) an intermolecular
coupling reaction to produce the triphenylene intermediate
(G3).
[0120] The triphenylene intermediate (G3) may undergo Step (ii) a
thionation reaction followed by an intramolecular cyclisation
reaction to afford the triphenylene derivatives (P3).
[0121] Step (ii) of the method may be performed using a thionating
agent, for example, Lawesson's reagent ammonium phosphorodithioate
or thiophosphoryl chloride with triethylamine.
[0122] For example, the method of synthesising triphenylene
derivatives (M) may comprise the formula:
##STR00015##
[0123] A yet further aspect of the invention provides a method of
synthesising polycyclic aromatic hydrocarbons, e.g. triphenylene
derivatives, (P4), the method comprising the following general
formula:
##STR00016## [0124] wherein (F4) represents a polycyclic aromatic
hydrocarbon core, (P4) represents a polycyclic aromatic hydrocarbon
derivative; [0125] p is an integer of 1 to 2; [0126] q is an
integer of 1 to 2; [0127] s is an integer of 1 to 4; [0128]
Y.sup.1, Y.sup.2, and Y.sup.3 independently represent one or more
of a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine
atom, a bromine atom, a carbon atom, an oxygen atom (e.g. an
alkylated oxygen atom), a nitrogen atom (e.g. an alkylated nitrogen
atom), a cyano group, a nitro group, an alkyl group and/or an aryl
group; [0129] G independently represents a substituted carbon atom;
[0130] (E) represents the reagent; R independently represents an
aromatic group and/or an aliphatic group; [0131] Z is one of an
oxygen atom, a derivatised oxygen atom, a chlorine atom, or a
bromine atom, or any good leaving group.
[0132] The method of synthesising triphenylene derivatives (P5) may
comprise the general formula:
##STR00017## [0133] wherein (F5) represents a triphenylene core,
(P5) represents a triphenylene derivative; [0134] A independently
represents a hydrogen atom, an aryl group, an alkyl group
comprising 1 to 20 carbons (e.g. 1 to 15 carbons, or 1 to 10
carbons, or 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 carbons); [0135] J
independently represent a hydrogen atom, a deuterium atom, a
fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom (e.g. an alkylated oxygen atom), a nitrogen atom (e.g.
an alkylated nitrogen atom), a cyano group, a nitro group, an alkyl
group and/or an aryl group (e.g. a phenol group). [0136] G
independently represents a substituted carbon atom; [0137] (E)
represents the reagent; [0138] R independently represents an
aromatic group and/or an aliphatic group; [0139] Z is one of an
oxygen atom, a derivatised oxygen atom, a chlorine atom, or a
bromine atom;
[0140] (F5) represents the triphenylene core, G is an alkyl,
hydrogen atom or aryl group, (E) represents the reagent, R is an
aromatic group and/or an aliphatic group, Z is one of an oxygen
atom, a derivatised oxygen atom, a chlorine atom, or a bromine
atom, and wherein the triphenylene core (F5) and the reagent (E)
undergo Step (i) an intermolecular coupling reaction to produce the
triphenylene intermediate (G5). The triphenylene intermediate (G5)
may undergo Step (ii) a thionation reaction followed by an
intramolecular cyclisation reaction to afford the triphenylene
derivatives (P5).
[0141] Step (ii) of the method may be performed using a thionating
agent, for example, Lawesson's reagent ammonium phosphorodithioate
or thiophosphoryl chloride with triethylamine.
[0142] The triphenylene core (F5) of the method of synthesising
triphenylene derivatives (P5) may comprise the formula (N):
##STR00018##
[0143] A yet further aspect of the invention provides a method of
synthesising of synthesising polycyclic aromatic hydrocarbon
derivatives (P6) comprising the general formula:
##STR00019## [0144] wherein (F6) represents a polycyclic aromatic
hydrocarbon core, (P6) represents a polycyclic aromatic hydrocarbon
derivative; [0145] p, q, and s are independently an integer of 1 to
2; [0146] Y.sup.1, Y.sup.2, and Y.sup.3 independently represent one
or more of a hydrogen atom, a deuterium atom, a fluorine atom, a
chlorine atom, a bromine atom, a carbon atom, an oxygen atom (e.g.
an alkylated oxygen atom), a nitrogen atom (e.g. an alkylated
nitrogen atom), a cyano group, a nitro group, an alkyl group and/or
an aryl group; [0147] G independently represents a substituted
carbon atom; [0148] (E) represents the reagent; [0149] R
independently represents an aromatic group and/or an aliphatic
group; [0150] Z is one of an oxygen atom, a derivatised oxygen
atom, a chlorine atom, or a bromine atom, or any good leaving
group.
[0151] The method of synthesising triphenylene derivatives (P7) may
comprise the general formula:
##STR00020## [0152] wherein (F7) represents a triphenylene core,
(P7) represents a triphenylene derivative; [0153] A independently
represents a hydrogen atom, an aryl group, an alkyl group
comprising 1 to 20 carbons (e.g. 1 to 15 carbons, or 1 to 10
carbons, or 10, 9, 8, 7, 6, 5, 4, 3, 2 or 1 carbons); [0154] J
independently represent a hydrogen atom, a deuterium atom, a
fluorine atom, a chlorine atom, a bromine atom, a carbon atom, an
oxygen atom (e.g. an alkylated oxygen atom), a nitrogen atom (e.g.
an alkylated nitrogen atom), a cyano group, a nitro group, an alkyl
group and/or an aryl group (e.g. a phenol group). [0155] G
independently represents a substituted carbon atom; [0156] (E)
represents the reagent; [0157] R independently represents an
aromatic group and/or an aliphatic group; [0158] Z is one of an
oxygen atom, a derivatised oxygen atom, a chlorine atom, or a
bromine atom.
[0159] (F7) represents the triphenylene core, G is an alkyl or aryl
group, (E) represents the reagent, R is an aromatic group and/or an
aliphatic group, Z is one of an oxygen atom, e.g. an OH group, a
derivatised oxygen atom, a chlorine atom, or a bromine atom, and
wherein the triphenylene core (F7) and the reagent (E) undergo Step
(i) an intermolecular coupling reaction to produce the triphenylene
intermediate (G7). The triphenylene intermediate (G7) may undergo
Step (ii) a thionation reaction followed by an intramolecular
cyclisation reaction to afford the triphenylene derivatives
(P7).
[0160] The thionation reaction may be performed using a thionating
agent, for example, Lawesson's reagent ammonium phosphorodithioate
or thiophosphoryl chloride with triethylamine.
[0161] The triphenylene core (F7) of the method of synthesising
triphenylene derivatives (P7) may comprise the formula (P):
##STR00021##
[0162] The method may further comprise a reagent to replace, in
situ, group Z with a good leaving group.
[0163] The reagent (E) may be a carboxylic acid, for example,
benzoic acid or a substituted benzoic acid. The method may further
comprise the use of a reagent and/or catalyst to form the
triphenylene intermediate, e.g. (J3), from the triphenylene core,
e.g. (H3). For example, the reagent may be dicyclohexylcarbodiimide
(DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC).
[0164] Step (i) of the method may further comprise a species to
replace group Z with a good leaving group, for example, the species
may be (diacetoxyiodo)benzene).
[0165] Alternatively, the reagent (E) may be an acyl chloride, for
example, benzyl chloride or a substituted benzyl chloride.
[0166] Step (i) of the method may comprise heating the triphenylene
core in a solvent, e.g. toluene, wherein Compound (E) is an acyl
chloride, i.e. Z is a chlorine atom.
[0167] Step (i) and Step (ii) may be performed as separate steps,
or may be performed in one single step, in a `one pot`
synthesis.
[0168] It is to be understood that the polycyclic aromatic
derivatives may be further functionalised to produce analogues. For
example, the polycyclic aromatic hydrocarbon derivatives, e.g. the
triphenylene derivatives, may undergo bromination, e.g. using
Br.sub.2, to add a bromine atom to one or more aromatic carbon
atoms. The bromine atom may act as a functional group to undergo
further chemical transformations, e.g. to functionalise the
polycyclic aromatic hydrocarbon derivatives with a phenol group. In
embodiments, J may represent a bromine atom and/or a phenol group.
The bromine atom and/or phenyl group may be used to further
functionalise the polycyclic aromatic hydrocarbon derivative.
[0169] Additionally or alternatively, the alkyl groups of one or
more of the alkoxy groups (e.g. the OC.sub.5H.sub.11 groups) may be
de-alkylated to form hydroxyl (e.g. phenol) groups (e.g. using
boron tribromide).
[0170] The polycyclic aromatic hydrocarbon derivatives may act as
bio-labels or bio-probes.
[0171] Within the scope of this application it is expressly
intended that the various aspects, embodiments, examples and
alternatives set out in the preceding paragraphs, in the claims
and/or in the following description and drawings, and in particular
the individual features thereof, may be taken independently or in
any combination. That is, all embodiments and/or features of any
embodiment can be combined in any way and/or combination, unless
such features are incompatible. For the avoidance of doubt, the
terms "may", "and/or", "e.g.", "for example" and any similar term
as used herein should be interpreted as non-limiting such that any
feature so-described need not be present. Indeed, any combination
of optional features is expressly envisaged without departing from
the scope of the invention, whether or not these are expressly
claimed. The applicant reserves the right to change any originally
filed claim or file any new claim accordingly, including the right
to amend any originally filed claim to depend from and/or
incorporate any feature of any other claim although not originally
claimed in that manner.
[0172] Embodiments of the invention will now be described by way of
example only with reference to the accompanying drawings in
which:
[0173] FIG. 1 is a representative structure of a series of
triphenylene derivatives according to some embodiments of the
invention;
[0174] FIG. 2 is a schematic synthetic route of the prior art to
the precursors of the triphenylene derivatives according to
embodiments of the invention;
[0175] FIG. 3 is a schematic synthetic route for the synthesis of
triphenylene derivatives according to embodiments of the invention,
as shown in FIG. 1;
[0176] FIG. 4 are examples of triphenylene derivatives according to
examples of the invention;
[0177] FIG. 5 is an absorption and emission spectra of Compound
1;
[0178] FIG. 6 is a graph showing electrical conductivity and
photoconductivity data for Compound 1;
[0179] FIG. 7 is an OLED according to a further aspect of the
invention.
[0180] Referring now to FIG. 1, there is shown a representative
structure of a triphenylene derivative series 100 according to some
embodiments of the invention. In this series, the R group is
changed to provide analogues of the triphenylene derivative series
100. The R group may be selected to alter the luminescent and/or
other advantageous properties of the triphenylene derivative series
100.
[0181] Referring now to FIG. 2, there is shown a schematic
synthetic route 200 of the prior art (N. Boden et. al. J. Mater.
Chem., 1995, 5, 2275) to produce Precursor 1, which is an amine
(2,3,6,7,10,11-hexakis(pentyloxy)-1-triphenylenylamine). The full
procedures to synthesise Precursor 1, starting from catechol 201,
is found in the prior art and are incorporated herein by
reference.
[0182] Referring now to FIG. 3, there is shown a schematic
synthetic route 300 for the formation of the triphenylene
derivative series 100 of the present invention. There is shown
Precursor 1, an acyl chloride 301, a triphenylene amide
intermediate 302, and the triphenylene derivative series 100. The
acyl chloride 301 comprises an R group, which is incorporated into
the oxazole moiety of the triphenylene derivative series 100. The R
group may be an alkyl group, or an aryl group, i.e. the carbon atom
bonded to the oxazole moiety in the triphenylene derivative series
100 may be either sp.sup.2 or sp.sup.a hybridised.
[0183] Advantageously, the method of FIG. 3 enables a huge number
of analogues of the triphenylene derivate 100 to be synthesised by
varying the R group of the acyl chloride 301 in the method 300. The
triphenylene derivative series 100 of the present invention exhibit
a number of desirable properties, in particular desirable
luminescent characteristics. Advantageously, the R group may be
altered to `tune` these properties. More advantageously, within the
known parameters of this invention, the R group may be specifically
selected to enable the `tuning` of the desirable luminescent
characteristics. This is demonstrated in detail in the section
below.
[0184] To further exemplify the invention, reference is also made
to the following non-limiting Example.
[0185] All compound names were generated using Chem Draw.RTM.
software.
[0186] Referring to FIG. 4 there is shown Examples (Compound 1) of
the triphenylene derivative series 100. The methods for
synthesising Compound 1 is described below.
Example 1--Method of Synthesising Compound 1
[0187] Compound 1 was synthesised using the following method. A
solution of Precursor 1 (100 mg, 0.132 mmol), benzoyl chloride (92
mg, 0.658 mmol) and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol)
in PhMe (5 mL) was heated to and held at reflux for 18 h under
N.sub.2. The reaction was cooled to room temperature and then
evaporated to dryness in vacuo purified via flash column
chromatography (silica, 60% CH.sub.2Cl.sub.2: 40% n-hexane) to
afford Compound 302 (R=Ph) as a brown solid (19 mg, 18%).
[0188] Compound 302 (R=Ph) had the following characterisation data:
.sup.1H NMR .delta.H: (300 MHz, CDCl.sub.3) 8.55 (1H, s), 8.45 (1H,
s), 8.07 (2H, d, J 7.5), 7.78 (1H, s), 7.74 (1H, s), 7.72 (1H, s),
7.71 (1H, s), 7.59 (1H, d, J 7.0), 7.54 (2H, t, J 7.4), 4.15 (10H,
d, J 52.3), 3.67-3.54 (2H, m), 2.00-1.85 (8H, m), 1.70-1.37 (20H,
m), 1.34-1.06 (8H, m), 1.02-0.90 (12H, m), 0.83 (3H, t, J 7.0),
0.75 (3H, t, J 7.1) ppm. .sup.13C NMR .delta.C: (100 MHz,
CDCl.sub.3) 174.6, 151.0, 149.7, 148.7, 148.4, 148.4, 144.0, 135.1,
131.7, 130.9, 128.5, 127.9, 126.6, 124.7, 124.2, 123.0, 122.6,
122.0, 110.3, 108.1, 107.7, 106.8, 106.7, 73.4, 70.1, 70.0, 69.5,
69.3, 68.8, 32.1, 30.1, 29.9, 29.6, 29.4, 29.3, 28.7, 28.5, 28.5,
28.1, 22.9, 22.7, 22.6, 14.3, 14.3, 14.1 ppm. MALDI m/z: 863.3
([M]+100%).
[0189] A solution of Compound 302 (R=Ph) (100 mg, 0.116 mmol) and
Lawesson's Reagent (175 mg, 0.658 mmol) in PhMe (5 mL) was heated
to and held at reflux for 48 h under N.sub.2. The reaction was
cooled to room temperature and then evaporated to dryness in vacuo.
The solid was then heated and held at 240.degree. C. for 15 mins
under N.sub.2. The crude black solid was then cooled to room
temperature and purified via flash column chromatography (silica,
40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 1 as a green
solid (17 mg, 19%).
[0190] The name for Compound 1 is
2,3,6,11,12-pentakis(pentyloxy)-8-phenyltriphenyleno[1,2-d]thiazole.
[0191] Compound 1 had the following characterisation data: .sup.1H
NMR .delta.H: (300 MHz, CDCl.sub.3) 10.51 (1H, s), 8.24-8.22 (2H,
m), 7.92-7.89 (3H, m), 7.76 (1H, s), 7.53-7.52 (3H, m), 4.43-4.26
(10H, m), 2.10-1.95 (10H, m), 1.66-1.57 (10H, m), 1.53-1.47 (10H,
m), 1.03-1.00 (15H, m) ppm. .sup.13C NMR OC: (100 MHz, CDCl.sub.3)
166.4, 152.5, 151.5, 150.2, 149.3, 148.3, 134.7, 130.9, 130.0,
129.3, 127.6, 125.7, 125.4, 124.7, 123.8, 119.0, 112.4, 108.9,
107.2, 106.9, 100.9, 70.3, 70.2, 69.7, 69.2, 69.1, 29.7, 29.6,
29.6, 29.5, 29.4, 28.8, 28.8, 28.8, 23.1, 23.0, 23.0, 23.0 23.0,
14.5, 14.5, 14.5, 14.5 ppm. MALDI m/z: 791.56 ([M]+ 100%).
[0192] Example 2--Method of Synthesising Compound 2 Compound 2 was
synthesised using the following method. A solution of Precursor 1
(100 mg, 0.132 mmol), 4-cyanobenzoyl chloride (109 mg, 0.658 mmol)
and N,N-diisopropylethylamine (0.1 mL, 0.574 mmol) in PhMe (5 mL)
was heated to and held at reflux for 18 h under N.sub.2. The
reaction was cooled to room temperature and then evaporated to
dryness in vacuo. The crude brown solid was added to a solution of
Lawesson's Reagent (175 mg, 0.658 mmol) in PhMe (5 mL) was heated
to and held at reflux for 48 h under N.sub.2. The reaction was
cooled to room temperature and then evaporated to dryness in vacuo.
The solid was then heated and held at 240.degree. C. for 15 mins
under N.sub.2. The crude black solid was then cooled to room
temperature and purified via flash column chromatography (silica,
40% CH.sub.2Cl.sub.2: 60% n-hexane) to afford Compound 2 as a
yellow solid (5 mg, 5%).
[0193] The name for Compound 2 is
4-(2,3,6,11,12-pentakis(pentyloxy)triphenyleno[1,2-d]thiazol-8-yl)benzoni-
trile.
[0194] Compound 2 had the following characterisation data: .sup.1H
NMR .delta.H: (300 MHz, CDCl.sub.3) 10.38 (1H, s), 8.31 (2H, d, J
8.4), 7.97-7.88 (4H, m), 7.79 (1H, d, J 8.5), 4.41-4.26 (10H, m),
2.06-1.95 (10H, m), 1.61-1.55 (10H, m), 1.51-1.44 (10H, m),
1.03-0.97 (15H, m) ppm. MALDI m/z: 816.9 ([M]+90%), 817.9 ([M+H]+
100%).
Properties of Triphenylene Derivative Series 100
[0195] The triphenylene derivative series 100 of the present
invention exhibits a number of advantageous properties that are
useful in many applications. Some of these advantageous properties
are demonstrated and described below in a non-limiting way.
[0196] Referring now to FIG. 5, there is shown an absorption and
emission spectra 500 of Compound 1. Compound 1 was dissolved in
ethyl acetate, and the absorption and emission was measured. The
absorption maxima was shown to be 274 nm, and the emission maxima
was shown to be 492 nm.
[0197] FIG. 6 is a graph 600 showing electrical conductivity and
photoconductivity data for Compound 1. The electrical conductivity
601 was measured at different temperatures for Compound 1. The
photoconductivity 602 was measured at different temperatures for
Compound 1 whilst irradiating with UV light at 350 nm.
[0198] Large Stokes Shift
[0199] It should be noted that by Stokes shift, we also mean a
`pseudo` Stokes shift. The IUPAC definition of the Stokes shift
requires that the difference in the band maxima of the absorption
and luminescence arise from the same electronic transition.
However, it is widely referred to in the literature in general
terms to mean the difference in excitation and emission
wavelengths, regardless of electronic transition.
[0200] Emission Across the Entire Visible Spectrum, which Varies
with R Group Structure
[0201] Advantageously, the emission spectra of the compounds of the
invention span a large portion of the visible spectrum. The R group
need not be limited to those disclosed, and may be any alkyl or
aryl group. In particular, variation of the R group with, for
example, a different aromatic hydrocarbon group has been shown to
result in a shift in the emission spectra. The shift in emission,
and consequently the resulting visible colour of a specific
triphenylene derivative, within the triphenylene derivative series
100, may be predicted with a good level of certainty for variation
of the R group. Advantageously, this provides a huge number of
analogues, for example wherein R is an aryl group, so that the
emission is a colour within the visible spectrum, and this visible
colour may be `tuned` by slight structural alteration to the R
group of the triphenylene derivative series 100 of the present
invention.
Application of Triphenylene Derivative Series 100 in
Electroluminescent Devices
[0202] The triphenylene derivatives of the present invention may
also be used in a functional layer of an OLED (Organic Light
Emitting Diode). It has been shown that the triphenylene
derivatives of the present invention may exhibit excellent
emitting, charge transporting, and/or charge blocking
abilities.
[0203] Referring now to FIG. 7 there is shown an OLED 700. The OLED
700 comprises the following successive layers: a substrate 701, an
anode 702, an optional hole transport layer 703, an optional
electron blocking layer 704, an emissive layer 705, an optional
hole blocking layer 706, an optional electron transport layer 707,
and a cathode 708.
[0204] Each layer described above may comprise any suitable
material known to those skilled in the art, and may comprise more
than one type of material or layer. For example, the substrate 701
may comprise glass, quartz, polymers, and so on. The thickness is
not critical and may be, for example, between 25 to 1000 microns
depending on the application of the device. The anode 702 may
comprise any electrically conductive material, e.g. metal, or a
conductive metal oxide such as ITO (indium tin oxide). The hole
transport layer 703 may comprise, for example,
1,4-bis[(1-naphthyphenyl)-amino]biphenyl (NPD). The emissive layer
705 may comprise aluminium tris(8-hydroxyquinoline). The hole
blocking layer 706 may comprise
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproine, BCP).
The electron transport layer 707 may comprise, for example, metal
chelates such as, for example, aluminium tris(8-hydroxyquinoline).
The cathode 708 may comprise any metal, for example, aluminium,
lithium, magnesium, and/or calcium.
[0205] The emissive layer 705 comprises the triphenylene
derivatives of the present invention, e.g. the triphenylene
derivative series 100.
[0206] The OLED 700 is fabricated in the following manner: [0207]
The anode 702 is patterned upon the clean substrate 701. [0208] The
substrate 701, which is patterned with the anode 702, is treated
with oxygen for 1 to 5 minutes. [0209] The substrate 701, which is
patterned with the anode 702, is placed in a thermal evaporator and
the pressure is reduced to below 6.times.10.sup.-6 torr. [0210] The
hole transport layer 703, the electron blocking layer 704, the
emissive layer 705, the hole blocking layer 706, the electron
transport layer 707, and the cathode 708 are successively formed in
the listed order by thermal evaporation.
[0211] It will be appreciated by those skilled in the art that
several variations to the aforementioned embodiments are envisaged
without departing from the scope of the invention. For example, the
R group of the triphenylene derivative series 100 and Precursor 1
need not be restricted to C.sub.5H.sub.11, and may be any stable
alkyl or aryl group capable of alkylating the phenol moiety of the
triphenylene moiety.
[0212] Advantageously, the triphenylene derivative series 100 of
the present invention may be further functionalised, for example,
by derivatisation of functional groups within the R group. This
provides the possibility of using the triphenylene derivative of
the present invention as biotags or probes, for example.
[0213] It will also be appreciated by those skilled in the art that
any number of combinations of the aforementioned features and/or
those shown in the appended drawings provide clear advantages over
the prior art and are therefore within the scope of the invention
described herein.
* * * * *